JP2002155085A - Method for producing dianhydrohexitol-bis-(4- acryloyloxy)acylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing dianhydrohexitol-bis-(4-acryloyloxy) acylate represented by general formula 2. SOLUTION: In a first process, dianhydrohexitol bisacylate represented by general formula 3 is biacylated using a 3-halopropionyl halide, yielding the corresponding dianhydrohexitol-bis-[3-halopropionyloxy]arylate and in a second process, two hydrogen halide molecules are cleaved from the dianhydrohexitol- bis-[3-halopropionyloxy]arylate with the aid of a base. Consequently, high-purity dianhydrohexitol-bis-(4-acryloyloxy)acylate represented by general formula 2 is inexpensively obtained by an industrially simple method in a high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing dianhydrohexit-bis- (4-acryloyloxy) acylate.

[0002]

BACKGROUND OF THE INVENTION Dianhydrohexit-bis- (4-
Acryloyloxy) acylates are known only as non-isolatable components of mixtures or in contaminated form.

The reaction of dianhydrohexite with acryloyloxy-substituted benzoyl chloride either directly or with the aid of auxiliary bases gives, depending on the reaction conditions, various amounts of the general formula 1: acryloyloxy- ( Aryl) _m- anhydrohexit- (aryl) _n -oxyacryloyl 1 wherein m and n are the same or different, but are at least 1 and the sum of m + n is greater than 2 A hydrohexite derivative results. The compounds of the general formula 1 are present as a mixture, the individual compounds of which are difficult to deliberately isolate and, based on their mixing properties, are highly viscous or processed in resinous form. Difficult substance. Said mixtures are only very difficult to use or cannot be used at all as chiral forms in liquid-crystalline compounds, which allow a precise and reproducible adjustment of the wavelength of the pigments produced thereby.

[0004]

It was therefore an object of the present invention to provide a process by which dianhydrohexit-bis- (4-acryloyloxy) acylate can be obtained in pure form.

[0005]

The above object is achieved by the present invention.

The object of the present invention is to provide a compound of the general formula 3:

[0007]

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[Wherein, X has the meaning of aryl]
Of the dianhydrohexit-bisacylate is twice acrylated with a 3-halogenpropionyl halide, wherein halogen represents chlorine or bromine, respectively, with the corresponding dianhydrohexit-bis- [3-halogenpropionyloxy -Allylate is formed, and in a second step from dianhydrohexit-bis- [3-halogenpropionyloxy] -arylate with a base
General formula 2: separating hydrogen halide twice

[0009]

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Wherein aryl represents a p-phenylene group or a 2,6-naphthylene group, optionally substituted by fluorine, in the process for the preparation of dianhydrohexit-bis- (4-acryloyloxy) acylate. is there.

According to this method, dianhydrohexit-bis- (4-acryloyloxy) acylate of the general formula 2 can be obtained in an industrially simple manner, at low cost, with high purity and good yield. In particular, in this process, the generation of by-products, such as the dianhydrohexite derivative of the general formula 1, is slight, clearly below 1% and can be reduced to traces. The pure dianhydrohexit-bis- (4-acryloyloxy) acylate of the general formula 2 crystallizes well. Thus, they are easily purified and isolated.

In the case of dianhydrohexit-bis- (4-acryloyloxy) acylate of the general formula 2, the wavy lines represent the arbitrarily selectable arrangement of the corresponding chemical bonds above and below the illustrated surface of the bicyclic compound. ing.

A suitable dianhydrohexite derivative is
Isoidite (= 1,4; 3,6-dianhydro-L-
Idit) and Isomannid (=
1,4; 3,6-dianhydro-D-mannit) and especially isosorbide (= 1,4; 3,6-dianhydro-D-glucit).

Isosorbide-2,5-bis- (4-acryloyloxy) benzoate is particularly preferred.

In the first step, a 3-chloropropionic acid halide is preferably used as the 3-halogenated propionic acid halide. Furthermore, in a second step, hydrogen chloride is particularly easily separated from the corresponding dianhydrohexit-bis- [3-bromopropionyloxy] arylate and dianhydrohexit-bis- [3-chloropropionyloxy] arylate. So 3-
Halogen propionic chloride is preferred.

In the first step, dianhydrohexit-2,5-bis- (hydroxyallylate) of the general formula 3 and a 3-halogenpropionic acid halide are charged, preferably in an inert solvent, preferably 10 ° C to 60 ° C, especially 20 ° C
The acylation is carried out twice with a base at a temperature between 40 ° C. and 40 ° C.

In the first step, dianhydrohexit-2,5-bis- (hydroxyallylate) of the general formula 3 is preferably added at from 70.degree. C. to 150.degree. C., in particular from 90.degree.
It is likewise advantageous to carry out the acylation directly at 25 ° C. and at standard pressure, with slow addition of the 3-halogenpropionic acid halide and thermal removal of the hydrogen halide gas.
The reaction can be facilitated by removal of HCl gas using a passed inert gas such as nitrogen or argon.

The combination of the various methods described above is likewise advantageous.

Inert solvents include aromatic hydrocarbons such as benzol, toluene, xylol or trimethylbenzene, aliphatic hydrocarbons such as benzene or cyclohexane, open-chain or cyclic ethers such as dibutyl ether, ethylene glycol dimethyl ether,
Tetrahydrofuran or anisole, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone or mixtures from the abovementioned solvents are possible. These solvents and solvent mixtures are preferably 0.10 M
It has a boiling point or boiling point range of at most 200 ° C. in Pa.

Examples of suitable bases are LiOH, NaOH,
KOH and amines. Preferred bases are tertiary amines, especially triethylamine, tributylamine or pyridine or mixtures thereof.

Advantageously, after a reaction time of from 2 to 10 hours, the reaction mixture is allowed to cool, and the amine hydrochloride formed, if any, is removed from the reaction mixture by filtration or extraction with water. The rest of the starting product can be extracted by extraction with a sodium hydrogen carbonate solution. Dianhydrohexit-2,5-bis-
[(3-Halogenpropionyloxy) arylate]
May slowly crystallize after drying and evaporation of the solvent and contain traces of dianhydrohexit-2,5-bis-[(acryloyloxy) acylate] of the general formula 2, optionally The result is a sticky crystal that can be recrystallized. For recrystallization, for example, ethyl acetate, M
TB and mixtures thereof are suitable.

For the second step, the isolated dianhydrohexit-2,5-bis-[(3-halogenpropionyloxy) arylate] is advantageously dissolved in an inert solvent or Purified solution of dianhydrohexit-2,5-bis-[(3-halogenpropionyloxy) arylate] from one step or dianhydrohexit-2,5-bis-[(3-halogenpropionyloxy) arylate] Is converted with the aid of a base to the desired end product of the general formula 2 under two separations of urea halides. In the second step, the same substances as in the first step are used as the solvent and the base.

The separation of the hydrogen halide in the second step is preferably carried out at from 40 ° C. to 100 ° C., in particular from 60 ° C. to 80 ° C.
Done in

For stabilization of the dianhydrohexit-2,5-bis- (acryloyloxy) acylate of the general formula 2 for premature polymerization, a stabilizing agent such as BHDMA is preferably used in the second step. Add before.

One advantageous variant of the method according to the invention is that
By integrating the two steps, dianhydrohexit-2,
The reaction consists in carrying out the reaction without isolating 5-bis-[(3-halogenpropionyloxy) arylate]. In this case, advantageously, the first step and the second step proceed sequentially when the reaction temperature rises.

The dianhydrohexit-bis acylate of the general formula 3 used in the first step is prepared from a mixture of a polar solvent and a nonpolar solvent and a free dianhydrohexite in a solvent selected from nonpolar solvents, from a strong acid. Can be esterified with a hydroxy-substituted aromatic carboxylic acid of the general formula 4: HO-CO-X-OH4 in the presence of a neutral catalyst and with the separation of the water of reaction formed. X in Equation 4
Has the meaning described above.

In one preferred embodiment, the general formula 3
The dianhydrohexit-bisacylate is prepared as described above, but is not isolated, but as described above, dianhydrohexit-2,5-bis-[(3-
Halogen propionyloxy) arylate] (first step) and preferably is isolated without isolation into dianhydrohexit-bis- (4-acryloyloxy) acylate of the general formula 2 (second step). In particular, general formula 3
Is used in the first step as a product suspension which occurs directly during the preparation.

The reaction is carried out at standard pressure (0.1 MPa) or, when using a suitable device, for example an autoclave,
It can also be carried out at elevated or low pressure.

All of the above symbols in the above formulas have their meanings independently of one another.

In the following examples, all amounts and percentages relate to mass and all pressures are 0.10 MPa unless otherwise indicated.
(Absolute) and all temperatures are 20 ° C.

HTP represents a helical twisting force, and the measure of the twisting force of a chiral body is [1 / μm].

BHDMA is 2,6-di-tert-butyl-
Represents 4- (dimethylaminomethyl) phenol.

MTB represents t-butyl methyl ether.

[0034]

EXAMPLE 1 Isosorbide-2,5-bis- [4- (3) from isosorbide-2,5-bis- (4-hydroxybenzoate)
-Chloropropionyloxy) benzoate] To 38.7 g (0.1 mol) of isosorbide-2,5-bis- (4-hydroxybenzoate) was added 50 m of toluene.
In 1 l, at 110 ° C., 26.7 g (0.21 mol) of 3-chloropropionyl chloride were added, stirred well and boiled at reflux with HCl separation for 6 hours. 90
C. and at 1013 to 15 hPa, the toluene is distilled off,
50 ml of ethyl acetate were added at 60 ° C. and the glassy precipitate was stirred at 20 ° C. in 200 ml of cyclohexane. After filtration and drying, the desired product was obtained in a yield of 49.5 g (87 of theory), which was already 2%
Of isosorbide-2,5-bis- (4-acryloyloxy) -benzoate and had a melting point of 96-97 ° C.

Example 2 Isosorbide from isosorbide-2,5-bis- [4- (3-chloropropionyloxy) benzoate]
Preparation of 2,5-bis- (4-acryloyloxy) benzoate 49.5 g of the product from Example 1 (0.087 mol 9
Stabilized with 0.1% noBHDMA and ethyl acetate 20
It was charged as a partial suspension in 0 ml and at 70 ° C. 20.2 g (0.20 mol) of triethylamine were slowly added, followed by stirring for 3.5 hours. The resulting triethylamine hydrochloride is subsequently washed at 60 ° C. with water and the amine excess is extracted with 3% hydrochloric acid,
Neutralized by washing with distilled water. After cooling to 15 ° C., the product which crystallized out was filtered off. After drying at 60 ° C. in vacuum,
The yield was 31.4 g (73% of theory). The product had a melting point of 124 ° C.

Example 3 Isosorbide from isosorbide-2,5-bis- (4-hydroxybenzoate) without isolation of the intermediate product
Production of 2,5-bis- (4-acryloyloxy) benzoate 38.7 g (0.1 mol) of isosorbide-2,5-bis- (4-hydroxybenzoate) was added to 200 ml of MTB.
25.4 g (0.2 mol) of 3-chloropropionyl chloride, charged in 0.1 ml of BHDMA and dissolved in 100 ml of toluene, are added and triethylamine (dissolved in 100 ml of toluene) 42.
2 g (0.42 mol) were added at 20-25 ° C. over 1.5 hours and then stirred at 56-60 ° C. for 1.5 hours.
After cooling to 20 ° C., it was washed with saturated sodium hydrogen carbonate solution, followed by 3% hydrochloric acid, then with water, the organic solvent was dried over sodium sulfate and then filtered off.

After distilling off the MTB at a maximum of 60 ° C. in vacuo, 200 ml of cyclohexane were added and the product was dissolved at 85 ° C. After cooling to 20 ° C., the product which crystallized out was filtered off and dried. The yield is 44.8 g.
(91% of theory), and the HTP is 52 [1 / μ
m].

Example 4 Isomanide from isosorbide-2,5-bis- (4-hydroxybenzoate) without isolation of the intermediate product
2,5-bis- (4-acryloyloxy) benzoic acid salt 36.6 g (0.25 mol) of isocyanide and 70 g (0.51 mol) of 4-hydroxybenzoic acid were added to toluene 2
In 00 ml, 6.4 g of 50% sulfuric acid and 12 g of diethylene glycol dimethyl ether were added and then esterified for 17 hours with water separator until the required guess was obtained. The product suspension is added at reflux temperature in 20 minutes to 3
66 g (0.52 mol) of -chloropropionyl chloride were added, followed by removal of the HCl at 110 ° C. for 2 hours under a slight stream of nitrogen. Toluol at 80 ° C
And distilled off at 50 hPa, and ethyl acetate 300m
1 was added. After stabilization with 0.08 g of BHDMA, at 30-40 ° C., 60.6 g of triethylamine
(0.6 mol) was added in 35 minutes, and the mixture was subsequently stirred at 60 ° C. for 2.5 hours. The resulting triethylamine hydrochloride was filtered off, after cooling to 20 ° C., the product crystallized out of the filtrate-crude solution in 16 hours.
After filtration, the crude product was taken up in 100 ml of ethyl acetate
After extraction of the solution with 3% hydrochloric acid, then saturated sodium bicarbonate solution and then twice with water,
It was dried over sodium sulfate and then crystallized at 10 ° C. after cooling. The product was filtered off, washed with methanol and then dried. Yield 32.2 g, corresponding to 25.9% of theory.

Fp: 132-134 ° C.

EXAMPLE 5 Isosorbide-2,5-bis-[(6-acryloyloxy) -naphthanoate-2] isosorbide-bis- (hydroxynaphthoate)
2 g (6.6 mol) were dissolved in 40 ml of acetic acid ethyl ester and 3-chloropropionyl chloride 1.9 was obtained.
2 g (15.13 mmol) are added and at 75 ° C. BH
After addition of 1 mg of DMA, 4.04 g (40 mmol) of triethylamine were added in 10 minutes. 2 at 78 ° C
After time, after cooling to 40 ° C., 10 ml of water are added,
The insoluble components were filtered off and the organic phase, after separation of the water, was washed with 10 ml of sodium hydrogen carbonate, then with 3% hydrochloric acid and then with water. After evaporation of the solvent under vacuum at 70 ° C., it was recrystallized from glacial acetic acid. The yield is 1.5 g (38.8 of theory)
%)Met. Fp: 171-172 ° C. HT of product
P was set to 54 [1 / μm] at 70 ° C.

 ──────────────────────────────────────────────────の Continuation of front page (71) Applicant 390009003 Zielstattstraβe 20, D-81379 Munchen, F.C. R. Germany (72) Inventor Norman Heberle Germany Federal Republic of Munich Willy Baltstraße 51a (72) Inventor Marx Creekbaum Federal Republic of Germany Munich Birker Strasse 27 F-term (reference) 4C071 AA01 BB01 CC12 DD04 EE05 FF15 HH05 KK14

Claims (5)

[Claims] In the first step, a compound represented by the general formula 3: Wherein X has the meaning of aryl, wherein the dianhydrohexit-bis acylate is acrylated twice with a 3-halogenpropionyl halide, wherein halogen represents chlorine or bromine, respectively, with the corresponding Dianhydrohexit-bis- [3-halogenpropionyloxy] -arylate is formed, and in a second step from dianhydrohexit-bis- [3-halogenpropionyloxy] -arylate with a base twice, General formula 2 for separating hydrogen halide: Wherein the aryl is p, optionally substituted with fluorine
-Represents a phenylene group or a 2,6-naphthylene group]. 2. The process according to claim 1, wherein in the first step isosorbide-bisacylate is used as dianhydrohexit-bisacylate of the general formula (3). 3. The method according to claim 1, wherein 3-chloropropionic chloride is used as the halogenated propionic halide in the first step. 4. The process according to claim 1, wherein isosorbide-2,5-bis- (4-acryloyloxy) benzoate is produced. 5. The process according to claim 1, wherein the two steps are integrated and the reaction is carried out without isolation of dianhydrohexit-2,5-bis-[(3-halogenpropionyloxy) arylate]. The method according to any one of the preceding claims.